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金属学报  2019, Vol. 55 Issue (6): 751-761    DOI: 10.11900/0412.1961.2018.00486
  本期目录 | 过刊浏览 |
Fe-Cu-Pb合金液-液相分离及废旧电路板混合金属分级分离与回收
陈斌1,2,何杰1,2(),孙小钧1,2,赵九洲1,2,江鸿翔1,张丽丽1,郝红日1
1. 中国科学院金属研究所 沈阳 110016
2. 中国科学技术大学材料科学与工程学院 沈阳 110016
Liquid-Liquid Phase Separation of Fe-Cu-Pb Alloy and Its Application in Metal Separation and Recycling of Waste Printed Circuit Boards
Bin CHEN1,2,Jie HE1,2(),Xiaojun SUN1,2,Jiuzhou ZHAO1,2,Hongxiang JIANG1,Lili ZHANG1,Hongri HAO1
1. Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
2. School of Materials Science and Engineering, University of Science and Technology of China, Shenyang 110016, China
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摘要: 

以废旧手机电路板为研究对象,采用热解技术使电路板金属与非金属解离,获得以Fe、Cu和Pb为主组分的混合金属。基于主组分为Fe、Cu和Pb,实验研究了(Fe0.4Cu0.6)100-xPbx三元合金的液-液相分离行为。结果表明,合适成分的Fe-Cu-Pb三元合金熔体在冷却过程中首先发生液-液相分离L→L(Fe)+L(Cu, Pb),待L(Fe)液相凝固后,剩余的液相L(Cu, Pb)再次发生液-液相分离L(Cu, Pb)→L(Cu)+L(Pb),最终主要形成富Fe、富Cu和富Pb三区分离结构。基于Fe-Cu-Pb合金液-液相分离凝固特征,设计了废旧电路板混合金属自组装分级分离系统,研究了混合金属中次组分Cr、Au、Cd等在主组分Fe、Cu和Pb中的富集行为,分析了离心超重条件对混合金属分离率和回收率的影响,建立了废旧手机电路板金属资源无害化回收处理新方法。

关键词 难混溶合金Fe-Cu-Pb合金液-液相分离废旧电路板金属分离与回收    
Abstract

The pyrolysis processing was carried out on the waste printed circuit boards (WPCBs) of mobile phones to dissociate metals from non-metals and obtain mixed metals with Fe, Cu and Pb as main components. Based on the main compositions of Fe, Cu and Pb, the liquid-liquid phase separation behavior of (Fe0.4Cu0.6)100-xPbx ternary alloy has been studied experimentally. The results show that the liquid-liquid phase separation of L→L(Fe)+L(Cu, Pb) may occur during the ternary Fe-Cu-Pb alloy melt cooling in the miscibility gap. After the liquid L(Fe) solidified, the secondary liquid-liquid phase separation L(Cu, Pb)→L(Cu)+L(Pb) takes place in the residual L(Cu, Pb) liquid phase, finally resulting in a three-zone separation structure. On the basis of the behavior of the liquid-liquid phase separation, a self-organized hierarchical separation system has been designed to separate and recycle these mixed metals from WPCBs. The enrichment behavior of the minor components like Cr, Au and Cd in the separation system was explored. The effect of super-gravity level on the metal separation and recycling rates has been discussed. As a result, a new harmless route has been established to recycle metal resources in WPCBs.

Key wordsimmiscible alloy    Fe-Cu-Pb alloy    liquid-liquid phase separation    waste printed circuit board    metal separation and recycling
收稿日期: 2018-10-30      出版日期: 2019-03-21
ZTFLH:  X705  
基金资助:国家自然科学基金项目(Nos.51574216);国家自然科学基金项目(51774264);国家自然科学基金项目(51374194);中国科学院金属研究所创新基金重点项目(No.SCJJ-2013-ZD-03);辽宁省自然科学基金项目(No.2015020172)
通讯作者: 何杰     E-mail: jiehe@imr.ac.cn
Corresponding author: Jie HE     E-mail: jiehe@imr.ac.cn
作者简介: 陈 斌,男,1991年生,博士生

引用本文:

陈斌,何杰,孙小钧,赵九洲,江鸿翔,张丽丽,郝红日. Fe-Cu-Pb合金液-液相分离及废旧电路板混合金属分级分离与回收[J]. 金属学报, 2019, 55(6): 751-761.
Bin CHEN,Jie HE,Xiaojun SUN,Jiuzhou ZHAO,Hongxiang JIANG,Lili ZHANG,Hongri HAO. Liquid-Liquid Phase Separation of Fe-Cu-Pb Alloy and Its Application in Metal Separation and Recycling of Waste Printed Circuit Boards. Acta Metall Sin, 2019, 55(6): 751-761.

链接本文:

http://www.ams.org.cn/CN/10.11900/0412.1961.2018.00486      或      http://www.ams.org.cn/CN/Y2019/V55/I6/751

图1  不同升温速率下废旧电路板的TG曲线
图2  热解前废旧手机电路板及热解后获得的混合金属
ElementCuFePbAuAgCrCoNiSiAlZnSnCdInBi
Content61.115.02.40.10.31.40.15.41.83.24.14.70.10.10.2
表1  废旧手机电路板混合金属组成
图3  (Fe0.4Cu0.6)100-xPbx三元合金的典型宏观分离形貌
图4  计算的不同Pb含量下Fe-Cu-Pb合金的组元液态不混溶区域
图5  三元(Fe0.4Cu0.6)72Pb28合金凝固过程示意图
MetalFeCuPbCrCoNiSiAuAgZnSnBiInCd
Fe--------------
Cu13-------------
Pb2915------------
Cr-11228-----------
Co-1617-4----------
Ni-2413-70---------
Si-35-1915-37-38-40--------
Au8-92077-30-------
Ag2823271915-20-6------
Zn4155-5-9-18-16-4-----
Sn1172100-4-11-10-31----
Bi26150241410-22241---
In1910-12072-10-11-230-1--
Cd17621762-13-11-21010-
表2  不同金属间的混合焓(ΔHA-B)[41]
图6  1473 K时次要金属在富Fe和富Cu液相中的分配系数的对数值lgKMCu/Fe以及其他学者的研究结果[27,48],及1233 K时添加和不添加Al作为捕集剂时次要金属在富Cu和富Pb液相中的分配系数的对数值lgKMCu/Pb
图7  超重力场中,MFeC-MPCB-MPb-MAl (质量比MFeC∶MPCB∶MPb∶MA=0.8∶1∶1.1∶0.1)、MFeC-MPCB (质量比MFeC∶MPCB=0.8∶1)和MCu-rich zone-MPb-MAl (质量比MCu-rich zone∶MPb∶MAl=1∶1.1∶0.1)铸锭切面的OM像(n=4500 r/min),及离心分离得到的Cu枝晶与富Pb物质
图8  离心转速(n)对铸锭富Fe区中Cu含量和富Cu区中Fe含量的影响
图9  不同转速下1473 K时富Fe液滴以及1233 K时富Pb液滴在Cu基体的运动速率(νS、ν'S)与液滴半径的关系
Separated substanceCrCoNiSiAgAuZnSnBiCdIn
Fe-rich94.993.680.893.7--3.24.1---
Cu-rich5.16.418.36.392.695.183.231.61.519.09.4
Pb-rich--0.9-7.44.913.664.398.581.090.6
表3  次要金属在不同分离物料中的回收率(H)
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